Spherical rubber chemicals and the method for preparing the same

ABSTRACT

The present invention provides spherical rubber chemicals and the method for preparing the same. The spherical rubber chemicals of the present invention include spherical antioxidants, spherical vulcanization agents, spherical processing aids, spherical reinforcing agents, or spherical adhesive agents. With the spherical rubber chemicals of the present invention, the shortcomings of powdery or semi-spherical rubber chemicals are overcome, including eliminating the dust pollution during granulation procedure and avoiding the raw material loss and the environmental pollution, while solving the quality problem of lower melting point of product caused by the presence of fine powder crystal. Furthermore, the resultant rubber chemicals has an improved smoothness of surface, which is helpful to improve the flowing and mixing behaviors of the rubber chemicals in mixing or open milling process with rubbers.

RELATED APPLICATIONS

This application is the U.S. National Stage of International ApplicationNo. PCT/CN2007/002953, filed Oct. 15, 2007, published in Chinese, andclaims priority under 35 U.S.C. §119 or 365 to Chinese Application No.200610135744.X, filed Oct. 17, 2006.

TECHNICAL FIELD

The present invention relates to spherical rubber chemicals and themethod for preparing the same, more specifically, to spherical rubberantioxidants, vulcanization agents, processing aids, reinforcing agentsand adhesive agents, especially to the spherical granules ofp-phenylenediamine type rubber antioxidantN-1,3-dimethylbutyl-N′-phenyl-p-phenylenediamine orN-isopropyl-N′-phenyl-p-phenylenediamine and the method for preparingthe same.

BACKGROUND ART

Rubber chemicals are important chemical materials in the rubberindustry, and they play an important role in improving the rubberperformance, such as upgrading the rubber quality and increasing therubber processing level. With the continuous progress in the rubberindustry, there is a higher demand for the general quality of rubberchemicals. At present, the rubber chemicals provided in market aregenerally of powdery or semispherical shape. The dust of powder rubberchemicals are likely to fly in the air, thereby causing loss of therubber chemicals and imparting adverse effects on the environment.

Currently, a common granulation method for rubber chemicals is therotary belt condensation granulating process with the followingoperating principle: utilizing the low melting point (or softeningpoint) characteristics of the material, the molten liquid material isdistributed evenly on a steel belt moving at a uniform speed below aspecial distributing device depending on the viscosity range of themolten material. Meanwhile, under forced cooling of a continuouslyspraying device provided under the steel belt, the material is cooledand solidified during the movement and transportation procedure, therebyachieving the purpose of continuous granulation and formation. Accordingto the material properties and the intended use, the distribution modeof intermittent drippling, continuous flowing and full-width overflowingmay be employed to obtain semisphere, bar and sheet product,respectively. The method has the following defects: 1) the coolingmedium removes heat from the molten liquid via the steel belt, and heatis transferred from the molten liquid to the steel belt and then to thecooling medium. So the heat transfer efficiency decreases significantly.Since the main heat transfer mode is heat conduction between the steelbelt surface and the cooling medium, the length of steel belt must beprolonged to increase the throughput, resulting in larger facility bulkand lower space utilization efficiency. 2) Since the liquid drops areformed on the steel belt, the resultant granules show a semispherical orflat shape. Although they have some advantages over the powdery rubberchemicals, the semispherical or flat rubber chemicals still havedefects. Specifically, some arris of sharp angle are formed at theboundary of spherical surface and flat surface in the granulationprocess, and they may be broken off by collision during packaging andtransportation and the reproduced powders also pollute the environment.In addition, the formed granules are scraped away from the steel belt atthe end of steel belt, in which process dust may fly in the air. Thepresence of fine powders may cause decrease of melting point in partialregions of the rubber chemicals. Also, the fine powders may jointogether, conglomerate and harden and the wholly or partially hardeningof the rubber chemical products makes a large bulk which deterioratesthe product quality seriously. Thus, there requires novel form of rubberchemicals which solve the above problems in the field of rubber chemicalgranulation.

SUMMARY OF THE INVENTION

The object of the invention is to improve the unfavorable granule shapein the existing granulation of rubber chemicals and solve the problemsof dust pollution caused by the rubber chemicals of powder, semisphereor other irregular shape in the granulation process, low heat transferefficiency, low production capability and relative high equipment costs,and to alleviate the quality problems of lower melting point in regionsof the product due to the presence of fine powder crystals and wholly orpartially hardening of the product due to joining, hardening andconglomeration of fine powders.

The present inventors have found in various studies that the rubberchemicals formed in spherical shape eliminate the defects of the powderyor semispherical rubber chemicals prepared according to the existingmanufacture processes. In contrast, the rubber chemicals according tothe present invention have a much larger number of granules passingthrough sieve and a significantly increased granulation rate of product,thereby preventing the dust pollution caused in the granulation processand avoiding the material loss and environmental pollution. In addition,the quality problems of lower melting point in regions of the productdue to the presence of fine powder crystals and wholly or partiallyhardening of the product due to joining, hardening and conglomeration offine powders are also solved. Meanwhile, the rubber chemical granuleshave a higher surface smoothness which is helpful for flowing and mixingof the rubber chemicals in mixing or open milling process with rubbers.The present invention is carried out accordingly.

Thus, the present invention provides novel spherical rubber chemicals,preferably the spherical granules of the rubber chemicals have anaverage diameter ranging from 0.2 mm to 10 mm.

The spherical rubber chemical according to the present inventionincludes spherical rubber antioxidants, spherical vulcanization agents,spherical processing aids, spherical reinforcing agents, and sphericaladhesive agents.

The spherical vulcanization agents include spherical2-mercaptobenzothiazole, dibenzothiazole disulfide,N-tert-butyl-2-benzothiazole sulphenamide, N-cyclohexyl-2-benzothiazolesulphenamide, N,N-dicyclohexyl-2-benzothiazole sulphenamide andN-oxidiethylene-2-benzothiazole sulphenamide.

The spherical vulcanization agents also includeN-tert-butyl-bis(2-benzothiazole) sulphenamide,N-cyclohexyl-bis(2-benzothiazole) sulphenamide, tetraisobutylaminothiuram monosulfide, tetraisobutylamino thiuram disulfide, tetrabenzylthiuram disulfide, tetramethyl thiuram disulfide, tetraethyl thiuramdisulfide, tetramethyl thiuram monosulfide, pentamethylenethiuramhexasulfide, N,N-dithiodicaprolactam,N-oxydiethylenethiocarbamoyl-N′-tert-butyl sulphenamide,diphenylguanidine, diorthotolylguanidine, and vulcanizing resins havinga softening point lower than or equal to 250° C., includingpara-tert-butylphenol formaldehyde resin, para-tert-octylphenolformaldehyde resin and para-(1,1,3,3-tetramethylbutyl)-phenolformaldehyde resin bromide.

The rubber antioxidants includeN-1,3-dimethylbutyl-N′-phenyl-p-phenylenediamine,N-isopropyl-N′-phenyl-p-phenylenediamine,N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine,2,2,4-trimethyl-1,2-dihydroquinoline polymer, octylated diphenylamine,N-phenyl-N′-cyclohexyl-p-phenylenediamine and 4-aminodiphenylamine,preferably spherical p-phenylenediamine antioxidantN-1,3-dimethylbutyl-N′-phenyl-p-phenylenediamine orN-isopropyl-N′-phenyl-p-phenylenediamine.

The rubber antioxidants also includeN-phenyl-N′-α-methylbenzyl-p-phenylenediamine,N,N′-ditolyl-p-phenylenediamine, and2,4,6-tri(N-1,4-dimethyl)pentyl-p-phenylenediamine-1,3,5-triazine.

The spherical processing aids according to the present invention includespherical anti-scorching agents, spherical plasticizers, sphericalhomogenizing agents, spherical tackifiers, and spherical releasingagents.

The spherical anti-scorching agents include sphericalN-cyclohexylthiophthalimide.

The spherical plasticizers include spherical Plasticizer A andpentachlorothiophenol.

The spherical homogenizing agents include spherical resins having asoftening point lower than or equal to 250° C., including a polymerresin of one or more saturated or unsaturated aromatic monomers,naphthenic monomers and aliphatic monomers, or a mixture of two or moresaturated or unsaturated aromatic resins, naphthenic resins andaliphatic resins.

The spherical tackifiers include spherical resins having a softeningpoint lower than or equal to 250° C., including petroleum resins, C9petroleum tackifier resins, complex C9 petroleum tackifier resins,modified petroleum alkylphenol resins, p-tert-butylphenol fomaldehyderesins, p-tert-octylphenol fomaldehyde resins, coumarone resins, orphenylethylene-indene resins.

The spherical releasing agents include spherical internal releasingagent AT-16.

The spherical adhesive agents include spherical cobalt decanoate, cobaltnaphthenate, and cobalt stearate.

The reinforcing agents include phenolic resins, oil-modified phenolicresins or petroleum resins having a softening point lower than or equalto 250° C.

Another aspect of the present invention provides a method for preparingthe above spherical rubber chemicals, comprising an overhead granulationstep, a cooling and forming step and a cooling liquid-removing step.

According to a preferable embodiment of the present invention, themethod of the present invention further comprises a pre-crystallizingstep prior to the overhead granulation step.

In a preferable embodiment of the present invention, in the overheadgranulation step, a material tank and a distribution plate are detachedfrom each other and are separated by a thermal insulating layer.

In another preferable embodiment of the present invention, in the headgranulation step, a heating and/or cooling medium is provided for thedistribution plate; small holes and intermediate holes are disposed fromtop to bottom in the distribution plate, the small holes have a diameterbetween 0.1 and 5 mm and the intermediate hole nozzles have a diameterbetween 0.2 and 10 mm.

According to a further preferable embodiment of the present invention,large holes are provided below the intermediate holes with a distance of0.5-5 mm between the inner wall of a large hole and the outer wall ofthe intermediate hole nozzle. Preferably, a chamfer angle is formed atthe lower end of the nozzle.

During the overhead granulation step, the material drips naturally bygravity, under pressure by reciprocating motion or under a constantpressure by a high viscosity feeding pump. Preferably, reciprocatingmotion facilitation is adopted.

During the overhead granulation step, the dripping rate from a nozzle is1-4 drops/second.

In another preferable embodiment of the present invention, a surfactantis added into the cooling liquid in a cooling tower and/or ultrasonicwave is applied thereto in the cooling and forming step. Preferably, thecooling liquid is at least one selected from the group consisting ofwater, aqueous ammonia, an aqueous solution of a salt and an organicsubstance. In some preferable embodiments of the present invention, thecooling liquid is selected from the group consisting of water, aqueousammonia, an aqueous solution of methanol, an aqueous solution of sodiumchloride, gasoline or acetone. Preferably, the surfactant is at leastone selected from the group consisting of polyethylene glycol ether,polypropylene glycol ether, fatty alcohol polyoxyethylene ether, alkylbenzene-sulfonate compounds, quaternary ammonium salt compounds, alkylalcohol ammonium type surfactants and betaine type surfactants.Preferably, the fatty alcohol in the fatty alcohol polyoxyethylene etherhas 6-18 carbon atoms and the polymerization degree of polyoxyethyleneis 3-25. Preferably, the betaine type surfactant is selected from agroup consisting of cocoamidopropyl betaine, dimethylalkyl betaine andN,N-dimethyl-N-alkoxymethylene betaine.

The term “spherical” as used herein refers to sphere or spheroid havinga diameter difference of ≦20%, and includes the sphere or spheroidhaving minor surface defects. The term “diameter difference” as usedherein refers to a percentage of the difference between the length of aline segment formed by linking two arbitrary points on the surface ofthe sphere or spheroid through the center of gravity of the sphere orspheroid and the average length of such line segments in respect to thesaid average length.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a flow chart showing formation of the spherical granules ofrubber chemicals according to a preferable embodiment of the presentinvention.

FIG. 2 is a schematic diagram of the distribution plate according to apreferable embodiment of the present invention, wherein “1” indicatesthe small hole, “2” indicates the intermediate hole, “3” indicates thenozzle, “4” indicates the large hole, i.e. a temperature-keeping hole,“5” indicates the temperature-keeping channel. In other embodiments ofthe present invention, the distribution plate may not include the largehole.

FIG. 3 is a schematic diagram showing three difference forms of nozzlesA, B and C used in the invention, wherein the nozzles A and C havechamfer angles at their lower ends, i.e. an outer chamfer angle at thelower end of nozzle A and an inner chamfer angle at the lower end ofnozzle C.

DETAILED EMBODIMENTS OF THE INVENTION

The present invention provides a spherical rubber chemical, wherein thepreferable average diameter of the spherical rubber chemical is 0.2-10mm. In addition, the present invention also provides the followingmethod for preparing the spherical rubber chemical. They will bedescribed in detail thereafter.

As shown in FIG. 1, raw material of the rubber chemical is pumped to thecooling and precrystallizing part, and after continuous circulating andcooling, a portion of the material reach a precrystallizing state and isdelivered to a temperature-keeping tank for molten material in the headpart for granulation. Alternatively, depending on its properties, thematerial may be fed directly into the temperature-keeping tank formolten material in the head part for granulation without theprecrystallizing step. The material is granulated with a designeddistribution plate. The extruded molten granules of spherical shape falldown into a cooling tower in which the material and the cooling liquidsufficiently exchange heat and at the same time the material solidifiesslowly into solid spherical granules. The resultant solid sphericalgranules are further treated to remove the cooling liquid, wherein mostcooling liquid may be removed by draining and then the sphericalgranules are dried to remove the remaining cooling liquid.

Before the overhead granulation, the material, especially that from theprecrystallizer, has very poor flowability since they are in a statebetween solid and liquid. And since the material has a high crystal seedconcentration but does not crystallize, it has a variable viscosityvarying from tens of CP to tens of thousands even million of CP. Thus,this requires a close control. Proper control over the viscosity rangeand over the crystallizing state of the material is a critical factor ingranulation.

In order to meet the high precision requirement of crystallizationtemperature control, especially in the overhead granulation step of therubber chemicals, we adopt multiple means to stabilize the processingparameter, the temperature. Specifically, a temperature-keeping means isprovided to the outside of the material tank, the distribution plate ismaintained at a constant temperature, and the temperature of pipelinesand the temperature of some moving parts are maintained. Varioustemperature-keeping means can be selected depending on differentproperties, for example, providing a heating and/or cooling mediumincluding steam, heat conducting oil and water of differenttemperatures, or adopting an electrically heating control system tocontrol strictly the precision of the temperature-keeping system,thereby keeping a constant temperature.

The material is formed into a spherical shape after dripping from thenozzle. The state of the material in dripping is important for theformation of granules. Material drops may be formed by naturallytrickling under gravity, under pressure by reciprocating motion or undera constant pressure applied on the material by a high viscosity feedingpump, so that the material is in a spherical shape after dripping fromthe nozzle. When the liquid material in the material tank has a veryhigh viscosity, the mass transfer and heat transfer are very difficult.A little longer retention time will cause solidification or partialcoagulation of the material. So an agitation means or a coil pipe may beused to improve the mass transfer and heat transfer. For a material withhigh crystal seed concentration and being prone to coagulation, drippingfacilitated by reciprocating motion is preferable. Any method andapparatus for pressing materials by reciprocating motion in the art canbe used in the present invention. In a preferable embodiment, areciprocating pump is connected to the material tank, and a coil pipe isdisposed in the material tank. A heating and/or cooling medium passesthrough the coil pipe to accurately control the temperature of thematerial. In an embodiment of the invention, a preferable heating and/orcooling medium is water. The coil pipe moves following the frequency ofthe reciprocating pump, so that the material in the material tank isheld in a moving state and does not coagulate while the dripping ofmaterial is facilitated by the reciprocating motion. In addition, thefrequency of the reciprocating pump is adjustable. Preferably, thedripping rate of the nozzle is controlled at 1-4 drops/second byadjusting the frequency of the reciprocating pump and more preferably,the dripping rate of the nozzle is controlled at 2-3 drops/second. Thus,the material will be drawn back as the reciprocating pump and coil pipemove upward, and when moving downward under a pressure, the material isextruded as spherical granules through the nozzle and falls down,thereby avoiding formation of material bar or jam of the nozzle.

Considering that the drops of material with low crystal seedconcentration are likely to break and conglutinate in water and that thematerials with high crystal seed concentration are likely to solidify toblock the nozzles, in the light of the characteristics of meltgranulation process, the material tank is designed to be separated fromthe distribution plate with a thermal insulating layer which hasopenings only at places corresponding to the nozzles to allow a liquidto pass through the nozzles. Therefore, the material tank may have adifferent temperature from the distribution plate and the heat transferbetween the material tank and the distribution plate is blocked. Thus,the temperature of the distribution plate can be adjusted according tothe state of material in the material tank, achieving the objective ofcontrolling the state of the material. This design has more flexibilityin regulation and controlling of the material and is more feasible inindustrial production.

Three different holes can be disposed in the distribution plate from topto bottom: small holes for controlling the flow rate, intermediate holeswith nozzles for dripping and formation of material, and large holes forshielding and temperature-keeping. Depending on the material condition,for example, for a material having a high crystal seed concentration andunlikely to coagulate, the temperature-keeping large holes can beomitted. Depending on the characteristics of products, the distributionplate preferably has a plurality of evenly-distributed small holes,intermediate holes, optional large holes and inner temperature-keepingchannels. The small holes have a diameter of 0.1-5 mm, the diameter ofthe intermediate hole nozzles depends on the required diameter ofgranules and is 0.2-10 mm, and the distance between the inner wall of alarge hole (i.e. a temperature-keeping hole) and the outer wall of anintermediate hole nozzle is 0.5-5 mm. The nozzle may have differentforms, for example the nozzle A, B and C shown in FIG. 3. Preferably,the nozzle has a chamfer angle at its lower end, and the preferablenozzles among A, B and C are nozzles A and C. The nozzle A has an outerchamfer angle at its lower end, and nozzle C has an inner chamfer angleat its lower end. More preferably, the nozzle is nozzle A which has anouter chamfer angle. Moreover, temperature-keeping channels are formedbetween the nozzles of the distribution plate. A heating and/or coolingmedium, such as steam, water or conducting oil, may be provided in thetemperature-keeping channels according to the temperature requirement tokeep a constant temperature of the distribution plate, therebymaintaining a stable material state.

In the cooling and forming step, different cooling liquids may beselected for the granulation of different products. The cooling liquidmay be water, aqueous ammonia, an aqueous solution of a salt, an organicsubstance and a mixture of two or more of the same. For example, thecooling liquid may be an aqueous solution of methanol, an aqueoussolution of sodium chloride, gasoline, acetone, etc.

In a preferable embodiment of the present invention, the rubber chemicalmaterial comes into contact directly with the cooling liquid in thecooling and forming step. Water is used as the cooling liquid so thatthe heat exchanging efficiency is increased significantly. Since waterhas a high specific heat and a large convective heat transfercoefficient, direct contact takes the advantage of the high heatexchange efficiency of water. Meanwhile, a liquid drop in waterexchanges heat with water via its all spherical surface, therebyachieving a three-dimensional heat transfer. While in the conventionalart, the cooling device is a steel belt and water spray which have lowerthermal conductivity and lower heat transfer coefficient. Moreover, theparticles are cooled via the contact surface of the steel belt, so theheat transfer efficiency is limited. In a preferable embodiment of thepresent invention, a cooling tower is used in the cooling and formingstep, so the equipment cost is reduced and the equipment efficiency perunit volume is increased significantly.

In another preferable embodiment of the present invention, thepreferable cooling liquid is an aqueous solution of methanol in thecooling and forming step. Since the aqueous solution of methanol has alower density, the rubber chemical granules will fall down faster in thecooling liquid and are prevented from floating on the liquid tofacilitate the formation of the granules.

During falling and cooling of the material, it is frequently found thatthe material has an insufficient hardness even it has formed intogranules. In the cooling and forming step, the temperature of thecooling liquid is very important for the solidification into solidgranules, and it is important to control the temperature of the coolingliquid properly. A suitable temperature of the cooling liquid may beselected according to the properties of the material, such as themelting point of the material. For example, in a further preferableembodiment of the present invention, the rubber chemical is ap-phenylenediamine type antioxidantN-1,3-dimethylbutyl-N′-phenyl-p-phenylenediamine orN-isopropyl-N′-phenyl-p-phenylenediamine, the cooling liquid is water,aqueous ammonia or an aqueous solution of methanol, preferably having atemperature of 10-40° C., and more preferably having a temperature of20-35° C.

In a preferable embodiment of the present invention, a surfactant issprayed onto the surface of the cooling liquid in the cooling andforming step. If the rubber chemical granules sedimentate with a lowsedimentation rate due to the presence of surface tension, it is likelythat a drop of the rubber chemical falls down before the previous dropsettles down, resulting in the superposition of two or even more dropswhich will impair the granule shape and the formation effect. In orderto prevent this phenomenon, a surfactant sprayed on the surface ofcooling liquid (such as water) or ultrasonic wave produced by anultrasonic generator is employed to reduce the surface tension tofacilitate the fast sedimentation of the granules, thereby solving theabove problem.

The surfactant which may be added into the cooling liquid to facilitatethe granule sedimentation includes, but not limited to, the followingexamples: polyethers, such as polyethylene glycol ether, polypropyleneglycol ether and fatty alcohol polyoxyethylene ether, and the mixturethereof; alkyl benzene sulfonate compounds; quaternary ammonium saltcompounds; alkyl alcohol ammonium type surfactants; as well as betainetype surfactants, such as cocoamidopropyl betaine, dimethylalkylbetaine, N,N-dimethyl-N-alkoxymethylene betaine, etc. Specifically, thesurfactant may be polyethylene glycol ether, such as polyethylene glycoldimethyl ether (having a molecular weight of 200-1000), polyethyleneglycol diethyl ether (having a molecular weight of 200-1000) andpolyethylene glycol methyl ethyl ether (having a molecular weight of200-1000); polypropylene glycol ether, such as polypropylene glycoldimethyl ether (having a molecular weight of 200-1000), polypropyleneglycol diethyl ether (having a molecular weight of 200-1000) andpolypropylene glycol methyl ethyl ether (having a molecular weight of200-1000); fatty alcohol polyoxyethylene ether, such as those having6-18 carbon atoms in the fatty alcohol part and 3-25 of polymerizationdegree of polyoxyethylene, for example, AEO-7, i.e. C₁₂H₂₅O(CH₂CH₂O)₇H.The surfactants of different performances can be selected for differentrubber chemicals and different cooling liquids.

Drying of the formed rubber chemical granules may utilize a fluidizedbed or a vibrated fluidized bed. A band-type drying process and commonoven drying process may also be used.

In the method according to the present invention, the rubber chemicalmaterial produces a spherical outer surface under the action of surfacetension or interfacial tension, so the resultant products have a goodsphericity, that is, they are substantially in a spherical shape. Theproducts thus obtained have an improved appearance quality, whichimproves the flowing and mixing behaviors of the rubber chemicals inmixing or open milling process with rubbers. According to the method ofthe present invention, the dust pollution of powdery materials isprevented, and the various dust pollution caused by break-off andcollision of the arris at the boundary of spherical surface and flatsurface of the semispherical granules are also avoided during thesubsequent procedures such as packaging, transportation, discharging andusing. With change in the granule shape, the present invention preventsthe reduction of melting point due to too much dust in the subsequentprocedures, so the quality problem of product is solved.

According to the method of the present invention, little dust isproduced in the granulation process. Although friction and collision mayoccur between the granules in some procedures, almost no dust isproduced before drying since a small amount of cooling liquid remains onthe surface of the granules and reduces the frictional strength largely.While some dust is produced in the drying process, since the fluidizedbed for drying is closed, the dust is collected and can not pollute theenvironment or affect the operator's health. The steel belt coolingprocess utilizes an open system and the granules must be scraped awayfrom the steel belt, the produced dust accumulates as time lapses andwill cause a lot of harm. In contrast, the granulation process accordingto the present invention makes a significant progress and improvement.

The rubber chemical granules obtained according to the method of thepresent invention have not only a spherical shape but also a smoothsurface. This is helpful to reduce the dust produced from frictionduring bag dumping and transportation.

The spherical rubber chemicals of the present invention as well as thespherical rubber chemicals that can be prepared according to the methodof the present invention include, but not limit to, the followingexamples: antioxidant 4020(N-1,3-dimethylbutyl-N′-phenyl-p-phenylenediamine), 4010NA(N-isopropyl-N′-phenyl-p-phenylenediamine), 4030(N,N-bis(1,4-dimethylpentyl)-p-phenylenediamine), RD(2,2,4-trimethyl-1,2-dihydroquinoline polymer), ODA (octylateddiphenylamine), 4010 (N-phenyl-N′-cyclohexyl-p-phenylenediamine),intermediate RT Base (4-aminodiphenylamine); vulcanization agents M(2-mercaptobenzothiazole), DM (dibenzothiazole disulfide),NS(N-tert-butyl-2-benzothiazole sulphenamide), CZ(N-cyclohexyl-2-benzothiazole sulphenamide), DZ(N,N-dicyclohexyl-2-benzothiazole sulphenamide), NOBS(N-oxidiethylene-2-benzothiazole sulphenamide), SPPD(N-phenyl-N′-α-methylbenzyl-p-phenylenediamine), DTPD(N,N′-ditolyl-p-phenylenediamine), TAPDA(2,4,6-tri-(N-1,4-dimethyl)pentyl-p-phenylenediamine-1,3,5-triazine),TBSI (N-tert-butyl-bis(2-benzothiazole) sulphenamide), CBBS(N-cyclohexyl-bis(2-benzothiazole) sulphenamide), Cure-riteIBM(tetraisobutylamino thiuram monosulfide), Cure-riteIBT(tetraisobutylamino thiuram disulfide), TBZTD (tetrabenzyl thiuramdisulfide), TMTD (tetramethyl thiuram disulfide), TETD (tetraethylthiuram disulfide), TMTM (tetramethyl thiuram monosulfide), DPTT(pentamethylenethiuram hexasulfide), DTDC (N,N-dithiodicaprolactam),OTTOS (N-oxydiethylenethiocarbamoyl-N′-tert-butyl sulphenamide), DPG(diphenylguanidine), DOTG (diorthotolylguanidine), para-tert-butylphenolformaldehyde resin, para-tert-octylphenol formaldehyde resin,bromomethylhydroxymethyl para-tert-octylphenol formaldehyde resin;anti-scorching agent CTP (N-cyclohexylthiophthalimide); Plasticizer A(mixture of high molecular fatty acids zinc soap),pentachlorothiophenol; homogenizing agents 40MS, 40MS(F), 60NS, 60NS(F)(composite resins of aromatic resin, naphthenic resin and aliphaticresin), TH10FL, TH20FL, 140, 145A, 260, H501; tackifiers petroleum resinPRF-80, PFR-90, PRF-100, PRF-110, C9 petroleum tackifier resin, complexC9 petroleum tackifier resin, modified alkylphenol resin TKM-M, TKM-T,TKM-O, p-tert-butylphenol fomaldehyde resin TKB-120, TKB-130, TKB-140,TKB-N, p-tert-octylphenol fomaldehyde resin TKO-70, TKO-80, TKO-90,TKO-100, TKO-110, coumarone resin, phenylethylene-indene resin type 90and 100; releasing agent AT-16 (mixture of a surfactant and fatty acidcalcium soap); adhesive agent including spherical cobalt decanoateRC-D20, cobalt naphthenate RC-10, cobalt stearate RC-S95; reinforcingagents reinforcing resin 205, oil-modified phenolic resin PF-P, PF-C,PF-O.

The preferable spherical rubber chemicals are antioxidants 4020(N-1,3-dimethylbutyl-N′-phenyl-p-phenylenediamine), 4010NA(N-isopropyl-N′-phenyl-p-phenylenediamine), SPPD(N-phenyl-N′-α-methylbenzyl-p-phenylenediamine) RD(2,2,4-trimethyl-1,2-dihydroquinoline polymer) (n=2-4); vulcanizationagents M (2-mercaptobenzothiazole), TBSI(N-tert-butyl-bis(2-benzothiazole) sulphenamide), CBBS(N-cyclohexyl-bis(2-benzothiazole) sulphenamide), OTTOS(N-oxydiethylenethiocarbamoyl-N′-tert-butyl sulphenamide), TBZTD(tetrabenzyl thiuram disulfide); anti-scorching agent CTP(N-cyclohexylthiophthalimide); Plasticizer A (mixture of high molecularzinc soap fatty acid); adhesive agent cobalt decanoate RC-D20, cobaltnaphthenate RC-10, cobalt stearate RC-S95; releasing agent AT-16(mixture of a surfactant and fatty acid calcium soap); homogenizingagents 40MS, 40MS(F), 60NS, 60NS(F) (composite resins of aromatic resin,naphthenic resin and aliphatic resin); tackifiers p-tert-octylphenolfomaldehyde resin TKO-70, TKO-80, TKO-90, TKO-100, TKO-110; reinforcingagents oil-modified phenolic resin PF-P, PF-C, PF-O.

The further preferable spherical rubber chemicals are antioxidant 4020(N-1,3-dimethylbutyl-N′-phenyl-p-phenylenediamine) and 4010NA(N-isopropyl-N′-phenyl-p-phenylenediamine).

EXAMPLE

The following examples are intended to illustrate the present invention,but do not limit the scope of the invention.

Example 1 Preparation of Spherical Granules ofN-1,3-dimethylbutyl-N′-phenyl-p-phenylenediamine

The molten material of preparedN-1,3-dimethylbutyl-N′-phenyl-p-phenylenediamine (4020) in a storagetank was pumped to the precrystallizing system with a pump capacity of600 kg/hour. The temperature of the cooling water for theprecrystallizer was maintained at 28-32° C. and the temperature of thewater for pipeline temperature-keeping was maintained at 46-48° C. Afterthe material in the precrystallizer reached the discharging state, adischarging pump was started to deliver the material into the materialtank. A jacket was provided outside the material tank for passing warmwater of 48-49° C. The material tank was separated from the distributionplate with a thermal insulating layer which had openings only at placescorresponding to the nozzles to allow the liquid material passingthrough the nozzles. Meanwhile, a reciprocating motion device over thematerial tank was actuated. A coil pipe was located under and connectedto the reciprocating device. There was warm water of 48-49° C. passingthrough the coil pipe. The material entered into the distribution plateand was granulated therein with a dripping rate of 2-3 drops/second. Thedistribution plate mainly included a plurality of equispaced holes andinner temperature-keeping channels, for example as shown in FIG. 2. Thetemperature-keeping channels were filled with warm water of 49-59° C.The small holes in the distribution plate had a diameter of 2.5 mm, theintermediate holes had a diameter of 4 mm, and the distance between theinner wall of the large holes for temperature-keeping and the outer wallof the nozzles was 2 mm. The nozzles had a chamfer angle at the lowerend, such as nozzle A shown in FIG. 3. After passing the nozzles, thematerial fell into a cooling tower with water as the cooling liquid. Asurfactant AEO-7 was sprayed onto the water surface to facilitate thesedimentation of material granules. The granules fell down from top tobottom and settled on the bottom of the cooling tower. The temperatureof the cooling water was controlled at 20-35° C. to solidify thegranules into solid spheres. The material flow then entered into thedraining procedure in which an oscillating screen with frequency of 40Hz was used. Then the material flow entered into the drying procedurewith a vibrated fluidized bed, in which the temperature of theair-drying fluidizing gas was 40° C. The final product was packed afterbeing dried to meeting the quality requirement. The produced sphericalgranules had good sphericity. One hundred (100) spherical granulescollected randomly were measured for their diameters with a verniercaliper and the average diameter of the spherical granules wasdetermined as 4.6 mm. The data exhibited a good normal distribution.

Example 2 Preparation of Spherical Granules ofN-isopropyl-N′-phenyl-p-phenylenediamine

The molten material of prepared N-isopropyl-N′-phenyl-p-phenylenediamine(4010NA) in a storage tank was pumped to the precrystallizing systemwith a pump capacity of 600 kg/hour. The temperature of the coolingwater for the precrystallizer was maintained at 55-60° C. and thetemperature of the water for pipeline temperature-keeping was maintainedat 75-80° C. After the material in the precrystallizer reached thedischarging state, a discharging pump was actuated to deliver thematerial into the material tank. A jacket was provided outside thematerial tank for passing warm water of 78-83° C. The material tank wasseparated from the distribution plate with a thermal insulating layerwhich had openings only at places corresponding to the nozzles to allowthe liquid material passing through the nozzles. Meanwhile, areciprocating motion device over the material tank was actuated. A coilpipe was located under and connected to the reciprocating device. Therewas warm water of 85-86° C. passing through the coil pipe. The materialentered into the distribution plate and was granulated therein with adripping rate of 2-3 drops/second. The distribution plate mainlyincluded a plurality of equispaced holes and inner temperature-keepingchannels, for example as shown in FIG. 2. The temperature-keepingchannels were filled with warm water of 75-85° C. The small holes in thedistribution plate had a diameter of 2.5 mm, the intermediate holes hada diameter of 4 mm, and the distance between the inner wall of the largeholes for temperature-keeping and the outer wall of the nozzle was 2 mm.The nozzles had a chamfer angle at the lower end, such as nozzle A shownin FIG. 3. After passing the nozzles, the material fell into a coolingtower with water as the cooling liquid. A surfactant AEO-7 was sprayedonto the water surface to facilitate the sedimentation of materialgranules. The granules fell down from top to bottom and settle on thebottom of the cooling tower. The temperature of cooling water wascontrolled at 20-35° C. to solidify the granules into solid spheres. Thematerial flow then entered into the draining and sieving procedure inwhich an oscillating screen with frequency of 40 Hz was used. Then thematerial flow entered into the drying procedure with a vibratedfluidized bed, in which the temperature of the air-drying fluidizing gaswas 70° C. The final product was packed after being dried to meet thequality requirement. The produced spherical granules had goodsphericity. One hundred (100) spherical granules randomly collected weremeasured for their diameters with a vernier caliper and the averagediameter of the spherical granules we determined as 4.6 mm. The dataexhibited a normal distribution.

Example 3 Preparation of Spherical Granules of2,2,4-trimethyl-1,2-dihydroquinoline polymer (n=2-4) (RD)

The molten material of prepared 2,2,4-trimethyl-1,2-dihydroquinolinepolymer (n=2-4) (RD) in a storage tank was pumped to theprecrystallizing system with a pump capacity of 600 kg/hour. Thetemperature of the cooling water for the precrystallizer was maintainedat 50-60° C. and the temperature of the water for pipelinetemperature-keeping was maintained at 70-80° C. After the material inthe precrystallizer reached the discharging state, a discharging pumpwas actuated to deliver the material into the material tank and theentire material tank was filled up with the material to maintain apressure of 0.1-0.5 MPa. A jacket was provided outside the material tankfor passing warm water of 75-85° C. The material tank was separated fromthe distribution plate with a thermal insulating layer which hadopenings only at places corresponding to the nozzles to allow the liquidmaterial passing through the nozzles. The material entered into thedistribution plate under the pressure produced from the discharging pumpand was granulated therein with a dripping rate of 2-3 drops/second. Thedistribution plate included a plurality of equispaced holes and innertemperature-keeping channels. The temperature-keeping channels werefilled with warm water of 80-85° C. The small holes in the distributionplate had a diameter of 2.5 mm, the intermediate holes had a diameter of4 mm, and there was no large hole for temperature-keeping. The nozzleshad a chamfer angle at the lower end, such as nozzle A shown in FIG. 3.After passing the nozzles, the material fell into a cooling tower withwater as the cooling liquid. A surfactant cocoamidopropyl betaine wassprayed onto the water surface to facilitate the sedimentation ofmaterial granules. The granules fell down from top to bottom and settledon the bottom of the cooling tower. The temperature of the cooling waterwas controlled at 50-70° C. to solidify the granules into solid spheres.The material flow then entered into the draining and sieving procedure,in which an oscillating screen with frequency of 40 Hz was used. Thenthe material flow entered into the drying procedure with a vibratedfluidized bed, in which the temperature of the air-drying fluidizing gaswas 70° C. The final product was packed after being dried to meetquality requirement. The produced spherical granules had good sphericityby visual examination. One hundred spherical granules randomly collectedwere measured for their diameters with a vernier caliper and the averagediameter of the spherical granules was determined as 5 mm. The dataexhibited a normal distribution.

Example 4 Preparation of Spherical Granules ofN-tert-butyl-2-benzothiazole sulphenamide (Accelerator NS)

The molten material of prepared N-tert-butyl-2-benzothiazolesulphenamide (accelerator NS) in a storage tank was pumped to thematerial tank while maintaining the temperature of the material at 110°C. Heat steam of 110-115° C. was provided outside the material tank. Thematerial tank was separated from the distribution plate with a thermalinsulating layer which had openings only at places corresponding to thenozzles to allow the liquid material passing through the nozzles.Meanwhile, a reciprocating motion device over the material tank wasactuated. A coil pipe was located under and connected to thereciprocating device. There was heat steam passing through the coilpipe. The material entered into the distribution plate and wasgranulated therein with a dripping rate of 2-3 drops/second. Thedistribution plate mainly included a plurality of equispaced holes andinner temperature-keeping channels. The temperature-keeping channelswere filled with heat steam. The small holes in the distribution platehad a diameter of 0.1 mm, the intermediate holes had a diameter of 0.25mm, and there was no large hole for temperature-keeping. The nozzles hada chamfer angle at the lower end, such as nozzle C shown in FIG. 3.After passing the nozzles, the material fell into a cooling tower inwhich water was used as the cooling liquid. A surfactant AEO-7 wassprayed onto the water surface to facilitate the sedimentation ofmaterial granules. The granules fell down from top to bottom and settledon the bottom of the cooling tower. The temperature of the cooling waterwas controlled at 60-70° C. to solidify the granules into solid spheres.The material flow then entered into the draining procedure, in which anoscillating screen with frequency of 40 Hz was used. Then the materialflow entered into the drying procedure with a vibrated fluidized bed, inwhich the temperature of the air-drying fluidizing gas was 40° C. Thefinal product was packed after being dried to meet quality requirement.The produced spherical granules had good sphericity. One hundredspherical granules randomly collected were measured for their diameterswith a vernier caliper and the average diameter of the sphericalgranules was determined as 0.2 mm. The data exhibited a good normaldistribution.

Example 5 Preparation of Spherical Granules ofN-1,3-dimethylbutyl-N′-phenyl-p-phenylenediamine

The molten material of preparedN-1,3-dimethylbutyl-N′-phenyl-p-phenylenediamine (4020) in a storagetank was pumped to the precrystallizing system with a pump capacity of600 kg/hour. The temperature of the cooling water for theprecrystallizer was maintained at 28-32° C. and the temperature of thewater for pipeline temperature-keeping was maintained at 46-48° C. Afterthe material in the precrystallizer reached the discharging state, adischarging pump was actuated to deliver the material into the materialtank. A jacket was provided outside the material tank for passing warmwater of 48-49° C. The material tank was separated from the distributionplate with a thermal insulating layer which had openings only at placescorresponding to the nozzles to allow the liquid material passingthrough the nozzles. Meanwhile, a reciprocating motion device over thematerial tank was actuated. A coil pipe was located under and connectedto the reciprocating device. There was warm water of 48-49° C. passingthrough the coil pipe. The material entered into the distribution plateand was granulated therein with a dripping rate of 2-3 drops/second. Thedistribution plate mainly included a plurality of equispaced holes andinner temperature-keeping channels, for example as shown in FIG. 2. Thetemperature-keeping channels were filled with warm water of 49-59° C.The small holes in the distribution plate had a diameter of 0.1 mm, theintermediate holes had a diameter of 0.2 mm, and the distance betweenthe inner wall of the large holes for temperature-keeping and the outerwall of the nozzles was 2 mm. The nozzles had a chamfer angle at itslower end, such as nozzle A shown in FIG. 3. After passing the nozzles,the material fell into a cooling tower with water as the cooling liquid.A surfactant AEO-7 was sprayed onto the water surface to facilitate thesedimentation of material granules. The granules fell down from top tobottom and settled on the bottom of the cooling tower. The temperatureof the cooling water was controlled at 20-35° C. to solidify thegranules into solid spheres. The material flow then entered into thedraining procedure, in which an oscillating screen with frequency of 40Hz was used. Then the material flow entered into the drying procedurewith a vibrated fluidized bed, the temperature of the air-dryingfluidizing gas is 40° C. The final product was packed after being driedto meet quality requirement. The produced spherical granules had goodsphericity. One hundred spherical granules randomly collected weremeasured for their diameters with a vernier caliper and the averagediameter of the spherical granules was determined as 0.22 mm. The dataexhibited a good normal distribution.

Example 6 Preparation of Spherical Granules ofN-1,3-dimethylbutyl-N′-phenyl-p-phenylenediamine

The molten material of preparedN-1,3-dimethylbutyl-N′-phenyl-p-phenylenediamine (4020) in a storagetank was pumped to the precrystallizing system with a pump capacity of600 kg/hour. The temperature of cooling water for the precrystallizerwas maintained at 28-32° C. and the temperature of the water forpipeline temperature-keeping was maintained at 46-48° C. After thematerial in the precrystallizer reached the discharging state, adischarging pump was actuated to deliver the material into the materialtank. A jacket was provided outside the material tank for passing warmwater of 48-49° C. The material tank was separated from the distributionplate with a thermal insulating layer which had openings only at placescorresponding to the nozzles to allow the liquid material passingthrough the nozzles. Meanwhile, a reciprocating motion device over thematerial tank was actuated. A coil pipe was located under and connectedto the reciprocating device. There was warm water of 48-49° C. passingthrough the coil pipe. The material entered into the distribution plateand was granulated therein with a dripping rate of 2-3 drops/second. Thedistribution plate mainly included a plurality of equispaced holes andinner temperature-keeping channels, for example as shown in FIG. 2. Thetemperature-keeping channels were filled with warm water of 49-59° C.The small holes in the distribution plate had a diameter of 5 mm, theintermediate holes had a diameter of 8 mm, and the distance between theinner wall of the large holes for temperature-keeping and the outer wallof the nozzles was 2 mm. The nozzle had a chamfer angle at the lowerend, such as nozzle A shown in FIG. 3. After passing the nozzles, thematerial fell into a cooling tower with water as the cooling liquid. Asurfactant AEO-7 was sprayed onto the water surface to facilitate thesedimentation of material granules. The granules fell down from top tobottom and settled on the bottom of the cooling tower. The temperatureof cooling water was controlled at 20-35° C. to solidify the granulesinto solid spheres. The material flow then entered into the drainingprocedure, in which an oscillating screen with frequency of 40 Hz wasused. Then the material flow entered into the drying procedure with avibrated fluidized bed, the temperature of the air-drying fluidizing gaswas 40° C. The final product was packed after being dried to meetquality requirement. The produced spherical granules had goodsphericity. One hundred spherical granules selected randomly weremeasured for their diameters with a vernier caliper and the averagediameter of the spherical granules was determined as 9.2 mm. The dataexhibited a good normal distribution.

Example 7 Preparation of SphericalN-isopropyl-N′-phenyl-p-phenylenediamine granules

The molten material of prepared N-isopropyl-N′-phenyl-p-phenylenediamine(4010NA) in a storage tank was pumped to the precrystallizing systemwith a pump capacity of 600 kg/hour. The temperature of the coolingwater for the precrystallizer was maintained at 55-60° C. and thetemperature of the water for pipeline temperature-keeping was maintainedat 75-80° C. After the material in the precrystallizer reached thedischarging state, a discharging pump was actuated to deliver thematerial into the material tank. A jacket was provided outside thematerial tank for passing warm water of 78-83° C. The material tank wasseparated from the distribution plate with a thermal insulating layerwhich had openings only at places corresponding to the nozzles to allowthe liquid material passing through the nozzles. Meanwhile, areciprocating motion device over the material tank was actuated. A coilpipe was located under and connected to the reciprocating device. Therewas warm water of 85-86° C. passing through the coil pipe. The materialentered into the distribution plate and was granulated therein with adripping rate of 2-3 drops/second. The distribution plate mainlyincluded a plurality of equispaced holes and inner temperature-keepingchannels, for example as shown in FIG. 2. The temperature-keepingchannels were filled with warm water of 75-85° C. The small holes in thedistribution plate had a diameter of 2.5 mm, the intermediate holes hada diameter of 4 mm, and the distance between the inner wall of the largehole for temperature-keeping and the outer wall of the nozzles was 2 mm.The nozzles had a chamfer angle at the lower end, such as nozzle A shownin FIG. 3. After passing the nozzles, the material fell into a coolingtower with water as the cooling liquid. Ultrasonic transducers wereequipped at four corners on the water surface to produce vibrationfacilitating the sedimentation of material granules. The granules felldown from top to bottom and settled on the bottom of the cooling tower.The temperature of the cooling water was controlled at 20-35° C. tosolidify the granules into solid spheres. The material flow then enteredinto the draining and sieving procedure, in which an oscillating screenwith frequency of 40 Hz was used. Then the material flow entered intothe drying procedure with a vibrated fluidized bed, the temperature ofthe air-drying fluidizing gas was 70° C. The final product was packedafter being dried to meet quality requirement. The produced sphericalgranules had good sphericity by visual examination. One hundredspherical granules selected randomly were measured for their diameterswith a vernier caliper and the average diameter of the sphericalgranules was determined as 4.6 mm. The data exhibited a normaldistribution.

Example 8 Preparation of Spherical Granules ofN-1,3-dimethylbutyl-N′-phenyl-p-phenylenediamine (with Aqueous Ammoniaas the Cooling Liquid)

The molten material of preparedN-1,3-dimethylbutyl-N′-phenyl-p-phenylenediamine (4020) in a storagetank was pumped to the precrystallizing system with a pump capacity of600 kg/hour. The temperature of the cooling water for theprecrystallizer was maintained at 28-32° C. and the temperature of thewater for pipeline temperature-keeping was maintained at 46-48° C. Afterthe material in the precrystallizer reached the discharging state, adischarging pump was used to deliver the material into the materialtank. A jacket was provided outside the material tank for passing warmwater of 48-49° C. The material tank was separated from the distributionplate with a thermal insulating layer which had openings only at placescorresponding to the nozzles to allow the liquid material passingthrough the nozzles. Meanwhile, a reciprocating motion device over thematerial tank was actuated. A coil pipe was located under and connectedto the reciprocating device. There was warm water of 48-49° C. passingthrough the coil pipe. The material entered into the distribution plateand was granulated therein with a dripping rate of 2-3 drops/second. Thedistribution plate mainly included a plurality of equispaced holes andinner temperature-keeping channels, for example as shown in FIG. 2. Thetemperature-keeping channels were filled with warm water of 49-59° C.The small holes in the distribution plate had a diameter of 3.5 mm, theintermediate holes had a diameter of 6 mm, and the distance between theinner wall of the large holes for temperature-keeping and the outer wallof the nozzles was 2 mm. The nozzles had a chamfer angle at the lowerend, such as nozzle A shown in FIG. 3. After passing the nozzles, thematerial fell into a cooling tower with aqueous ammonia of 6% (w/w) asthe cooling liquid. A surfactant AEO-7 was sprayed onto the liquidsurface to facilitate the sedimentation of material granules. Thegranules fell down from top to bottom and settled on the bottom of thecooling tower. The temperature of cooling water was controlled at 20-35°C. to solidify the granules into solid spheres. The material flow thenentered into the draining procedure, in which an oscillating screen withfrequency of 40 Hz was used. Then the material flow entered into thedrying procedure with a vibrated fluidized bed, the temperature of theair-drying fluidizing gas was 40° C. The final product was packed afterbeing dried to meet quality requirement. The produced spherical granuleshad good sphericity. One hundred spherical granules selected randomlywere measured for their diameters with a vernier caliper and the averagediameter of the spherical granules was 6.6 mm. The data exhibited a goodnormal distribution.

Example 9 Preparation of Spherical Granules ofN-1,3-dimethylbutyl-N′-phenyl-p-phenylenediamine (with Aqueous Solutionof Methanol as the Cooling Liquid)

The molten material of preparedN-1,3-dimethylbutyl-N′-phenyl-p-phenylenediamine (4020) in a storagetank was pumped to the precrystallizing system with a pump capacity of600 kg/hour. The temperature of the cooling water for theprecrystallizer was maintained at 28-32° C. and the temperature of thewater for pipeline temperature-keeping was maintained at 46-48° C. Afterthe material in the precrystallizer reached the discharging state, adischarging pump was actuated to deliver the material into the materialtank. A jacket was provided outside the material tank for passing warmwater of 48-49° C. The material tank was separated from the distributionplate with a thermal insulating layer which had openings only at placescorresponding to the nozzles to allow the liquid material passingthrough the nozzles. Meanwhile, a reciprocating motion device over thematerial tank was actuated. A coil pipe was located under and connectedto the reciprocating device. There was warm water of 48-49° C. passingthrough the coil pipe. The material entered into the distribution plateand was granulated therein with a dripping rate of 2-3 drops/second. Thedistribution plate mainly included a plurality of equispaced holes andinner temperature-keeping channels, for example as shown in FIG. 2. Thetemperature-keeping channels were filled with warm water of 49-59° C.The small holes in the distribution plate had a diameter of 1.0 mm, theintermediate holes had a diameter of 3 mm, and the distance between theinner wall of the large holes for temperature-keeping and the outer wallof the nozzles was 2 mm. The nozzles had a chamfer angle at its lowerend, such as nozzle A shown in FIG. 3. After passing the nozzles, thematerial fell into a cooling tower with an aqueous solution of methanolcontaining 20% (w/w) methanol as the cooling liquid. A surfactantcocoamidopropyl betaine was sprayed onto the liquid surface tofacilitate the sedimentation of material granules. The granules felldown from top to bottom and settle on the bottom of the cooling tower.The temperature of the cooling water was controlled at 20-35° C. tosolidify the granules into solid spheres. The material flow then enteredinto the draining procedure, in which an oscillating screen withfrequency of 40 Hz was used. Then the material flow entered into thedrying procedure with a vibrated fluidized bed, in which the temperatureof the air-drying fluidizing gas was 40° C. The final product was packedafter being dried to meet quality requirement. The produced sphericalgranules had good sphericity. One hundred spherical granules selectedrandomly were measured for their diameters with a vernier caliper andthe average diameter of the spherical granules was determined as 3.2 mm.The data exhibits a good normal distribution.

Example 10 Preparation of Spherical Granules ofN-tert-butyl-bis(2-benzothiazole) sulphenamide (Accelerator TBSI)(Melting Point: 130-133° C.)

The molten material of prepared N-tert-butyl-bis(2-benzothiazole)sulphenamide (accelerator TBSI) in a storage tank was pumped to thematerial tank while maintaining the material temperature at 135° C. Heatconducting oil of 135-140° C. was provided outside the material tank.The material tank was separated from the distribution plate with athermal insulating layer which had openings only at places correspondingto the nozzles to allow the liquid material passing through the nozzles.Meanwhile, a reciprocating motion device over the material tank wasactuated. A coil pipe was located under and connected to thereciprocating device. There was heat conducting oil passing through thecoil pipe. The material entered into the distribution plate and wasgranulated therein with a dripping rate of 2-3 drops/second. Thedistribution plate mainly included a plurality of equispaced holes andinner temperature-keeping channels for passing the heat conducting oil.The small holes in the distribution plate had a diameter of 2.5 mm, theintermediate holes had a diameter of 4 mm, and there was no large holefor temperature-keeping. The nozzles had a chamfer angle at the lowerend, such as nozzle C shown in FIG. 3. After passing the nozzles, thematerial fell into a cooling tower with water as the cooling liquid. Asurfactant AEO-7 was sprayed onto the water surface to facilitate thesedimentation of material granules. The granules fell down from top tobottom and settled on the bottom of the cooling tower. The temperatureof the cooling water was controlled at 60-70° C. to solidify thegranules into solid spheres. The material flow then entered into thedraining procedure, in which an oscillating screen with frequency of 40Hz was used. Then the material flow entered into the drying procedurewith a vibrated fluidized bed, the temperature of the air-dryingfluidizing gas was 40° C. The final product was packed after being driedto meet quality requirement. The produced spherical granules had goodsphericity. One hundred spherical granules selected randomly weremeasured for their diameters with a vernier caliper and the averagediameter of the spherical granules was 4.5 mm. The data exhibited a goodnormal distribution.

Example 11 Preparation of Spherical Granules of tetrabenzyl thiuramdisulfide (Accelerator TBZTD) (Melting Point: 130° C.)

The molten material of prepared tetrabenzyl thiuram disulfide(accelerator TBZTD) in a storage tank was pumped to the material tankwhile maintaining the material temperature at 132° C. Heat conductingoil of 133-135° C. was provided outside the material tank. The materialtank was separated from the distribution plate with a thermal insulatinglayer which had openings only at places corresponding to the nozzles toallow the liquid material passing through the nozzles. Meanwhile, areciprocating motion device over the material tank was actuated. A coilpipe was located under and connected to the reciprocating device. Therewas heat conducting oil passing through the coil pipe. The materialentered into the distribution plate and was granulated therein with adripping rate of 2-3 drops/second. The distribution plate mainlyincluded a plurality of equispaced holes and inner temperature-keepingchannels for passing heat conducting oil. The small holes in thedistribution plate had a diameter of 2.5 mm, the intermediate holes hada diameter of 4 mm, and the distance between the inner wall of the largeholes for temperature-keeping and the outer wall of the nozzles was 2mm. The nozzles had a chamfer angle at the lower end, such as nozzle Cshown in FIG. 3. After passing the nozzles, the material fell into acooling tower with water as the cooling liquid. A surfactant AEO-7 wassprayed onto the water surface to facilitate the sedimentation ofmaterial granules. The granules fell down from top to bottom and settledon the bottom of the cooling tower. The temperature of the cooling waterwas controlled at 60-70° C. to solidify the granules into solid spheres.The material flow then entered into the draining procedure, in which anoscillating screen with frequency of 40 Hz was used. Then the materialflow entered into the drying procedure with a vibrated fluidized bed, inwhich the temperature of the air-drying fluidizing gas was 40° C. Thefinal product was packed after being dried to meet quality requirement.The produced spherical granules had good sphericity. One hundredspherical granules selected randomly were measured for their diameterswith a vernier caliper and the average diameter of the sphericalgranules was 4.8 mm. The data exhibited a good normal distribution.

Example 12 Preparation of Spherical Granules ofN-phenyl-N′-α-methylbenzyl-p-phenylenediamine (SPPD) (Melting Point:54.8° C.)

The molten material of preparedN-phenyl-N′-α-methylbenzyl-p-phenylenediamine (SPPD) in a storage tankwas pumped to the precrystallizing system with a pump capacity of 600kg/hour. The temperature of cooling water for the precrystallizer wasmaintained at 65-75° C. and the temperature of the water for pipelinetemperature-keeping was maintained at 86-90° C. After the material inthe precrystallizer reached the discharging state, a discharging pumpwas actuated to deliver the material into the material tank. A jacketwas provided outside the material tank for passing warm water of 88-93°C. The material tank was separated from the distribution plate with athermal insulating layer which had openings only at places correspondingto the nozzles to allow the liquid material passing through the nozzles.Meanwhile, a reciprocating motion device over the material tank wasactuated. A coil pipe was located under and connected to thereciprocating device. There was warm water of 85-86° C. passing throughthe coil pipe. The material entered into the distribution plate and wasgranulated therein with a dripping rate of 2-3 drops/second. Thedistribution plate mainly included a plurality of equispaced holes andinner temperature-keeping channels, for example as shown in FIG. 2. Thetemperature-keeping channels were filled with warm water of 86-90° C.The small holes in the distribution plate had a diameter of 2.5 mm, theintermediate holes had a diameter of 4 mm, and a distance between theinner wall of a large warm-keeping hole and the outer wall of a nozzlewas 2 mm. The nozzle has a chamfer angle at its lower end, such asnozzle A shown in FIG. 3. After passing the nozzles, the material fallsinto a cooling tower with water as the cooling liquid. A surfactantAEO-7 was sprayed onto the water surface to facilitate the sedimentationof material granules. The granules fall down from top to bottom andsettle on the bottom of the cooling tower. The temperature of coolingwater was controlled at 20-35° C. to solidify the granules into solidspheres. The material flow then entered into the draining and sievingprocedure, in which an oscillating screen with frequency of 40 Hz wasused. Then the material flow entered into the drying procedure with avibrated fluidized bed, the temperature of air-drying fluidizing gas was75° C. The final product was packed after being dried to meet qualityrequirement. The produced spherical granules had good sphericity byvisual examination. One hundred spherical granules selected randomlywere measured for their diameters with a vernier caliper and thecalculated average diameter of spherical granules was 4.4 mm. The dataexhibits a normal distribution.

Example 13 Preparation of Spherical N-cyclohexylthiophthalimide (CTP)Granules (Melting Point ≧90° C.)

The molten material of prepared N-cyclohexylthiophthalimide (CTP) in astorage tank was pumped to the material tank while maintaining thematerial temperature at 93° C. Warm water of 92-95° C. was providedoutside the material tank. The material tank was separated from thedistribution plate with a thermal insulating layer which merely hasopenings corresponding to the nozzles to allow the liquid material topass through the nozzles. Meanwhile, a reciprocating device over thematerial tank was actuated. A coil pipe was located under and connectedto the reciprocating device. There was warm water of 90-95° C. passingthrough the coil pipe. The material enters into the distribution plateand was granulated therein with a dripping rate of 2-3 drops/second. Thedistribution plate mainly includes a plurality of equispaced holes andinner warm-keeping channels for passing warm water of 95-100° C. Thesmall holes in the distribution plate had a diameter of 2.5 mm, theintermediate holes had a diameter of 4 mm, and the distance between theinner wall of the large holes for temperature-keeping and the outer wallof the nozzles was 2 mm. The nozzles had a chamfer angle at the lowerend, such as nozzle C shown in FIG. 3. After passing the nozzles, thematerial fell into a cooling tower with water as the cooling liquid. Asurfactant AEO-7 was sprayed onto the water surface to facilitate thesedimentation of material granules. The granules fell down from top tobottom and settled on the bottom of the cooling tower. The temperatureof the cooling water was controlled at 55-60° C. to solidify thegranules into solid spheres. The material flow then entered into thedraining procedure, in which an oscillating screen with frequency of 40Hz was used. Then the material flow entered into the drying procedurewith a vibrated fluidized bed, in which the temperature of theair-drying fluidizing gas was 35° C. The final product was packed afterbeing dried to meet quality requirement. The produced spherical granuleshad good sphericity. One hundred spherical granules selected randomlywere measured for their diameters with a vernier caliper and the averagediameter of spherical granules was 5 mm. The data exhibited a goodnormal distribution.

Example 14 Preparation of Spherical Granules of Cobalt Stearate RC-S95(Adhesive Agent) (Softening Point; 80-100° C.)

The molten material of prepared cobalt stearate RC-S95 (adhesive agent)in a storage tank was pumped to the material tank while maintaining thematerial temperature at 105° C. Heating steam of 105-110° C. wasprovided outside the material tank. The material tank was separated fromthe distribution plate with a thermal insulating layer which hadopenings only at places corresponding to the nozzles to allow the liquidmaterial passing through the nozzles. Meanwhile, a reciprocating motiondevice over the material tank was actuated. A coil pipe was locatedunder and connected to the reciprocating device. There was heating steampassing through the coil pipe. The material entered into thedistribution plate and was granulated therein with a dripping rate of2-3 drops/second. The distribution plate mainly included a plurality ofequispaced holes and inner warm-keeping channels for passing heatingsteam. The small holes in the distribution plate had a diameter of 2.5mm, the intermediate holes had a diameter of 4 mm, and there was nolarge holes for temperature-keeping hole. The nozzles had a chamferangle at the lower end, such as nozzle C shown in FIG. 3. After passingthe nozzles, the material fell into a cooling tower in which water wasused as the cooling liquid. A surfactant AEO-7 was sprayed onto thewater surface to facilitate the sedimentation of material granules. Thegranules fell down from top to bottom and settle on the bottom of thecooling tower. The temperature of cooling water was controlled at 60-70°C. to solidify the granules into solid spheres. The material flow thenentered into the draining procedure, in which an oscillating screen withfrequency of 40 Hz was used. Then the material flow entered into thedrying procedure with a vibrated fluidized bed, the temperature ofair-drying fluidizing gas was 60° C. The final product was packed afterbeing dried to meet quality requirement. The produced spherical granuleshad good sphericity. One hundred spherical granules selected randomlywere measured for their diameters with a vernier caliper and the averagediameter of spherical granules was determined as 4.8 mm. The dataexhibited a good normal distribution.

Example 15 Preparation of Spherical Granules of Plasticizer A (Mixtureof High Molecular Fatty Acid Zinc Soap) (Melting Point: 98-104° C.)

The prepared mixture of high molecular fatty acid zinc soap (PlasticizerA) in a storage tank was pumped to the material tank while maintainingthe material temperature at 105° C. Heating steam of 105-115° C. wasprovided outside the material tank. The material tank was separated fromthe distribution plate with a thermal insulating layer which hadopenings only at places corresponding to the nozzles to allow the liquidmaterial passing through the nozzles. Meanwhile, a reciprocating motiondevice over the material tank was actuated. A coil pipe was locatedunder and connected to the reciprocating device. There was heating steampassing through the coil pipe. The material entered into thedistribution plate and was granulated therein with a dripping rate of2-3 drops/second. The distribution plate mainly included a plurality ofequispaced holes and inner temperature-keeping channels for passingheating steam. The small holes in the distribution plate had a diameterof 2.5 mm, the intermediate holes had a diameter of 4 mm, and there wasno large hole for temperature-keeping. The nozzles had a chamfer angleat the lower end, such as nozzle C shown in FIG. 3. After passing thenozzles, the material fell into a cooling tower with water as thecooling liquid. Ultrasonic transducers were equipped at four corners onthe water surface to produce vibration for facilitating thesedimentation of material granules. The granules fell down from top tobottom and settled on the bottom of the cooling tower. The temperatureof cooling water was controlled at 60-70° C. to solidify the granulesinto solid spheres. The material flow then entered into the drainingprocedure, in which an oscillating screen with frequency of 40 Hz wasused. Then the material flow entered into the drying procedure with avibrated fluidized bed, in which the temperature of air-dryingfluidizing gas was 60° C. The final product was packed after being driedto meet quality requirement. The produced spherical granules had goodsphericity. One hundred (100) spherical granules selected randomly weremeasured for their diameters with a vernier caliper and the averagediameter of the spherical granules was determined as 4.7 mm. The dataexhibited a good normal distribution.

Example 16 Preparation of Spherical Granules of Composite Resin (40MS)Composed of an Aromatic Resin, a Naphthenic Resin and an Aliphatic Resin(Softening Point: 50-60° C.)

The prepared composite resin (40MS) composed of an aromatic resin, anaphthenic resin and an aliphatic resin in a storage tank was pumped tothe material tank while maintaining the material temperature at 60° C.Warm water of 60-65° C. was provided outside the material tank. Thematerial tank was separated from the distribution plate with a thermalinsulating layer which had openings only at places corresponding to thenozzles to allow the liquid material passing through the nozzles.Meanwhile, a high-viscosity pump over the material tank was actuated. Acoil pipe was located under and connected to the pump. There was warmwater of 60-63° C. passing through the coil pipe. The material enteredinto the distribution plate and was granulated therein with a drippingrate of 2-3 drops/second. The distribution plate mainly included aplurality of equispaced holes and inner temperature-keeping channels forpassing warm water of 65-68° C. The small holes in the distributionplate had a diameter of 2.5 mm, the intermediate holes had a diameter of4 mm, and there was no large hole for temperature-keeping. The nozzleshad a chamfer angle at the lower end, such as nozzle C shown in FIG. 3.After passing the nozzles, the material fell into a cooling tower withwater as the cooling liquid. Ultrasonic transducers were equipped atfour corners on the water surface to produce vibration for facilitatingthe sedimentation of material granules. The granules fell down from topto bottom and settled on the bottom of the cooling tower. Thetemperature of cooling water was controlled at 20-35° C. to solidify thegranules into solid spheres. The material flow then entered into thedraining procedure, in which an oscillating screen with frequency of 40Hz was used. Then the material flow entered into the drying procedurewith a vibrated fluidized bed, in which the temperature of theair-drying fluidizing gas was 40° C. The final product was packed afterbeing dried to meet quality requirement. The produced spherical granuleshad good sphericity. One hundred spherical granules selected randomlywere measured for their diameters with a vernier caliper and the averagediameter of the spherical granules was determined as 4.6 mm. The dataexhibited a good normal distribution.

Example 17 Preparation of Spherical Granules of Para-Tert-OctylphenolFormaldehyde Resin (TKO-70) (Softening Point: 70-85° C.)

The prepared para-tert-octylphenol formaldehyde resin (TKO-70) in astorage tank was pumped to the material tank while maintaining thematerial temperature at 85° C. Warm water of 85-88° C. was providedoutside the material tank. The material tank was separated from thedistribution plate with a thermal insulating layer which had openingsonly at places corresponding to the nozzles to allow the liquid materialpassing through the nozzles. Meanwhile, a high-viscosity pump over thematerial tank was actuated. A coil pipe was located under and connectedto the pump. There was warm water of 85-88° C. passing through the coilpipe. The material entered into the distribution plate and wasgranulated therein with a dripping rate of 2-3 drops/second. Thedistribution plate mainly included a plurality of equispaced holes andinner temperature-keeping channels for passing warm water of 85-90° C.The small holes in the distribution plate had a diameter of 2.5 mm, theintermediate holes had a diameter of 4 mm, and there was no large holefor temperature-keeping. The nozzle had a chamfer angle at the lowerend, such as nozzle C shown in FIG. 3. After passing the nozzles, thematerial fell into a cooling tower with water as the cooling liquid.Ultrasonic transducers were equipped at four corners on the watersurface to produce vibration for facilitating the sedimentation ofmaterial granules. The granules fell down from top to bottom and settledon the bottom of the cooling tower. The temperature of cooling water wascontrolled at 20-35° C. to solidify the granules into solid spheres. Thematerial flow then entered into the draining procedure, in which anoscillating screen with frequency of 40 Hz was used. Then the materialflow entered into the drying procedure with a vibrated fluidized bed, inwhich the temperature of the air-drying fluidizing gas was 40° C. Thefinal product was packed after being dried to meet quality requirement.The produced spherical granules had good sphericity. One hundredspherical granules selected randomly were measured for their diameterswith a vernier caliper and the average diameter of the sphericalgranules was determined as 5 mm. The data exhibited a good normaldistribution.

Example 18 Preparation of Spherical Granules of Oil-Modified PhenolicResin (PF-P) (Softening Point: 75-90° C.)

The prepared oil-modified phenolic resin (PF-P) in a storage tank waspumped to the material tank while maintaining the material temperatureat 90° C. Warm water of 90-95° C. was provided outside the materialtank. The material tank was separated from the distribution plate with athermal insulating layer which had openings only at places correspondingto the nozzles to allow the liquid material passing through the nozzles.Meanwhile, a high-viscosity pump over the material tank was actuated. Acoil pipe was located under and connected to the pimp. There was warmwater of 90-95° C. passing through the coil pipe. The material enteredinto the distribution plate and was granulated therein with a drippingrate of 2-3 drops/second. The distribution plate mainly included aplurality of equispaced holes and inner temperature-keeping channels forpassing warm water of 90-98° C. The small holes in the distributionplate had a diameter of 2.5 mm, the intermediate holes had a diameter of4 mm, and there was no large hole for temperature-keeping. The nozzleshad a chamfer angle at the lower end, such as nozzle C shown in FIG. 3.After passing the nozzles, the material fell into a cooling tower withwater as the cooling liquid. Ultrasonic transducers were equipped atfour corners on the water surface to produce vibration for facilitatingthe sedimentation of material granules. The granules fell down from topto bottom and settled on the bottom of the cooling tower. Thetemperature of the cooling water was controlled at 20-35° C. to solidifythe granules into solid spheres. The material flow then entered into thedraining procedure, in which an oscillating screen with frequency of 40Hz was used. Then the material flow entered into the drying procedurewith a vibrated fluidized bed, the temperature of air-drying fluidizinggas was 40° C. The final product was packed after being dried to meetquality requirement.

The produced spherical granules had good sphericity. One hundredspherical granules selected randomly were measured for their diameterswith a vernier caliper and the average diameter of the sphericalgranules was determined as 4.8 mm. The data exhibited a good normaldistribution.

Example 19 Preparation of Spherical Granules of Internal Releasing AgentAT-16 (a Mixture of a Surfactant and Fatty Acid Calcium Soap) (SofteningPoint: 85-100° C.)

The molten material of a prepared mixture of a surfactant and fatty acidcalcium soap in a storage tank was pumped to the material tank whilemaintaining the material temperature at 105° C. Heating steam of105-110° C. was provided outside the material tank. The material tankwas separated from the distribution plate with a thermal insulatinglayer which had openings only at places corresponding to the nozzles toallow the liquid material passing through the nozzles. Meanwhile, areciprocating motion device over the material tank was actuated. A coilpipe was located under and connected to the reciprocating device. Therewas heating steam passing through the coil pipe. The material enteredinto the distribution plate and was granulated therein with a drippingrate of 2-3 drops/second. The distribution plate mainly included aplurality of equispaced holes and inner warm-keeping channels forpassing heating steam. The small holes in the distribution plate had adiameter of 2.5 mm, the intermediate holes had a diameter of 4 mm, andthere was no large hole for temperature-keeping. The nozzles had achamfer angle at the lower end, such as nozzle C shown in FIG. 3. Afterpassing the nozzles, the material fell into a cooling tower with wateras the cooling liquid. A surfactant AEO-7 was sprayed onto the watersurface to facilitate the sedimentation of material granules. Thegranules fell down from top to bottom and settled on the bottom of thecooling tower. The temperature of cooling water was controlled at 60-70°C. to solidify the granules into solid spheres. The material flow thenentered into the draining procedure, in which an oscillating screen withfrequency of 40 Hz was used. Then the material flow entered into thedrying procedure with a vibrated fluidized bed, in which the temperatureof the air-drying fluidizing gas was 60° C. The final product was packedafter being dried to meet quality requirement. The produced sphericalgranules had good sphericity. One hundred spherical granules selectedrandomly were measured for their diameters with a vernier caliper andthe average diameter of the spherical granules was determined as 5.1 mm.The data exhibited a good normal distribution.

1. A method for preparing spherical rubber chemicals, comprising anoverhead granulation step, a step of cooling and forming in a coolingliquid and a cooling liquid-removing step, wherein, in the overheadgranulation step, a material tank and a distribution plate are detachedfrom each other and are separated by a thermal insulating layer.
 2. Themethod according to claim 1, wherein further comprising apre-crystallizing step prior to the overhead granulation step.
 3. Themethod according to claim 1, wherein, in the overhead granulation step,a heating and/or cooling medium is provided for the distribution plate,small holes and intermediate holes are disposed from top to bottom inthe distribution plate, the small holes have a diameter of 0.1-5 mm andthe intermediate hole nozzles have a diameter of 0.2-10 mm.
 4. Themethod according to claim 3, wherein large holes are disposed below theintermediate holes with a distance of 0.5-5 mm between the inner wall ofa large hole and the outer wall of a intermediate hole nozzle.
 5. Themethod according to any one of claim 1, wherein, in the overheadgranulation step, a chamfer angle is disposed at the lower end of thenozzle.
 6. The method according to any one of claim 1, wherein, in theoverhead granulation step, the material drips naturally by gravity,under pressure by a reciprocating motion or under a constant pressure bya high viscosity feeding pump.
 7. The method according to claim 6,wherein dripping under pressure by a reciprocating motion is adopted inthe overhead granulation step.
 8. The method according to any one ofclaim 1, wherein, in the overhead granulation step, the dripping ratefrom a nozzle is 1-4 drops/second.
 9. The method according to any one ofclaim 1, wherein, in the cooling and forming step, a surfactant is addedinto the cooling liquid in a cooling tower and/or ultrasonic wave isapplied to the cooling liquid.
 10. The method according to claim 9,wherein the cooling liquid is at least one selected from the groupconsisting of water, aqueous ammonia, an aqueous solution of a salt andan organic substance.
 11. The method according to claim 10, wherein thecooling liquid is selected from the group consisting of water, aqueousammonia, an aqueous solution of methanol, an aqueous solution of sodiumchloride, gasoline or acetone.
 12. The method according to claim 9,wherein the surfactant is at least one selected from the groupconsisting of polyethylene glycol ether, polypropylene glycol ether,fatty alcohol polyoxyethylene ether, alkyl benzene sulfonate compound,quaternary ammonium salt compound, alkyl alcohol ammonium typesurfactant and betaine type surfactant.
 13. The method according toclaim 12, wherein the fatty alcohol in the fatty alcohol polyoxyethyleneether has 6-18 carbon atoms and the polymerization degree ofpolyoxyethylene is 3-25.
 14. The method according to claim 12, whereinthe betaine type surfactant is selected from a group consisting ofcocoamidopropyl betaine, dimethylalkyl betaine andN,N-dimethyl-N-alkoxymethylene betaine.